Processing for photographic silver halide light-sensitive element

ABSTRACT

WHEREIN Z represents an atom necessary to complete a heterocyclic ring, R represents a lower alkyl group or a substituted alkyl group, Ar represents a phenyl group or a substituted phenyl group, X represents an acid residual group, and n is 0 or 1, the n being 0 when the compound forms an internal salt.   In a method of processing a photographic silver halide lightsensitive element wherein in the development processing steps of said photographic silver halide light-sensitive element, the improvement comprising processing the exposed photographic silver halide light-sensitive element in the presence of an aldehydetype hardening agent and a compound represented by the formula

D (DENSITY) United States Patent Hara et al.

[451 Mar. 28, 1972 [541 PROCESSING FOR PHOTOGRAPHIC SILVER HALIDELIGHT-SENSITIVE ELEMENT [72] inventors: Hikoharu l-lara; Tadao l-latano,both of Kanagawa, Japan [73] Assignee: Fuji Photo Film Co., Ltd.,Kanagawa, Japan [22] Filed: July 23,1969

[21] Appl.No.: 844,129

301 Foreign Application Priority pm July 23, 1968 Japan ..43/52069 52]U.S.Cl. 9 6 /50Pl,96 /6 6- s1 lnt.Cl. ..G03c/26,G03c5/30' [58] FieldolSearch ..96/50,50PT,66.5,109,111, 96/102,140

[56] References Cited UNITED STATES PATENTS 2,320,654 6/1943 Riester..'...96/102 2,494,032 1/1950 Brooker.... ....96/102 2,901,351 8/1959Van Pee ...96/109 3,071,465 1/1963 Dersch et a1 ..96/665 PrimaryExaminerNorman G. Torchin Assistant Examiner-Mary F. KelleyAtromeySughrue, Rothwell, Mion, Zinn & Macpeak -[57] ABSTRACT In amethod of processing a photographic silver halide lightsensitive elementwherein in the development processing steps of said photographic silverhalide light-sensitive element, the improvement comprising processingthe exposed photographic siiver halide light-sensitive element in thepresence of an aldehyde-type hardening agent and a compound representedby the formula 14 Claims, 2 Drawing Figures DEVELOPED FOR 25 SEC AT 39CLog E (EXPOSURE AMT)- DEVELOPED FOR 5OSEC ,7 AT 39C D (DENSITY) N a; 'o

Log E (EXPOSURE AMT) PATENTEDmzs 1972 D (DENSITY) SHEEI10F2 FIG. I I

I DEVELOPED FOR 25 SEC AT 39C LOg E (EXPOSURE AMT).

INVENTOR! HIKQHARU HARA TADAO HATANO l Z4, M

A ORNEYS PATENTEDHARZB I912 3.652.277

SHEET 2 or 2 FIG. 2

DEVELOPED FOR 5OSEC AT 39C DXDENSITY) '9 Log E (EXPOSURE AMT INVENTORSHIKGMRU HARA TADAO HATANO Ala/. W, M BY z-MK 4 M MK ATTORNEYS 1PROCESSING FOR PHOTOGRAPI'IIC SILVER HALIDE LIGHT-SENSITIVE ELEMENTBACKGROUND OF THE INVENTION 1. Field of the Invention I The presentinvention relates to a method for processing photographic silver halidelight-sensitive elements and more particularly to a method forprocessing photographic silver halide light-sensitive elements using analdehyde-containing gelatin hardening agent and an antifoggant.

2. Description of Prior Art As a'method of efiiciently conducting thedevelopment of photographic'silver halide light-sensitive elements,there is known a so-called high temperature, high speed developingprocess by using a high temperature developer or other high temperatureprocessing solutions and such a process is effectively applied tovarious photographic silver halide light-sensitive elements.

However, as light-sensitive elements are processed at a high temperaturein such a conventional process, the mechanical developing step forphotographic silver halide light-sensitive elements, in the processingsolution an aldehyde-type hardening agent and a compound represented bythe general formu- Ia,

cyclic ring, R represents a lower alkyl group or a substituted alkylgroup, Ar represents a phenyl group or a substituted I phenyl group,Xrepresents an acid residual group, and n is strength of the emulsionlayers of the'light-sensitive elements in the high temperature developeror other processing solution must be prevented from being degraded.Therefore, it is necessary to increase the mechanical strength of theemulsion layer before development or during development and maintain themechanical strength thereof throughout the development.

For this purpose, there has been proposed a method in which aphotographic silver halide light-sensitive element is, beforedevelopment, subjected to a prehardening processing in a prehardeningsolution containing an aldehyde type hardening agent. The aldehydecompound remaining unreacted in the emulsion layer is removed by waterwashing or is made harmless by processing it in a solution beforedevelopment.

Such a method has the advantages that the processing time is shortenedby the high temperature development and the efficiency of the processingis improved but has the disadvantage that the nurnber of the processingsteps is greater than those in the usual method.

The disadvantage is caused by the use of an aldehyde compound as thehardening agent, for example; when an aldehyde, particularly adialdehyde, is added to a developer, the formation of fog of a black andwhite photographic film or a photographic color film processed in thedeveloper is remarkably increased. The formation of the fog caused bythe addition of such an aldehyde can be prevented by using a strongantifoggant such as benztriazole or mercatobenztetrazole. However, asthe use of such an antifoggant strongly supresses the progress ofdevelopment at the same time, the sensitivity of the emulsion is greatlydecreased.

BRIEF DESCRIPTION OF THE DRAWINGS FIGS. 1 and 2 show the amount of fogoccuring in various films after being processed in various developersolutions.

SUMMARY OF THE INVENTION Thus, an object of the present invention is toprovide a process for processing a light-exposed photographic silverhalide light-sensitive element without forming fog.

Another object of this invention is to provide a process fo preventingthe formation of fog caused by processing'a photographic silver halidelight-sensitive element in a processing solution containing analdehyde-type hardening agent.

A further object of this invention is to provide a process fordeveloping a photographic silver halide light-sensitive element withoutreducing the developing speed and the sensitivity of emulsion.

The present inventors have investigated the methods of achieving theabove-mentioned objects and, as a result thereof, have found that theaforesaid objects can be achieved by utilizing the present invention.More specifically, the above objects of this invention can be achievedby incorporating, in a or 1, said n being 0 when the compound is aninternal salt.

DETAILED DESCRIPTION OF THE INVENTION In the above-mentioned generalformula, as the lower alkyl group R, the following may be used: a methylgroup, an ethyl group, a propyl group and a butyl group and as thesubstituted alkyl group, a carboxymethyl group, a B-carboxyethyl group,a 'y-carboxypropyl group, a fl-hydroxyethyl group, a B-acetoxyethylgroup, a B-sulfoethyl group, a 'y-sulfobutyl group, a 8- sulfobutylgroup, a methoxyethyl group and the like. Also, as the substitutedphenyl group Ar the following are examples: phenyl groups substituted bya lower alkyl group; a hydroxyl group, an alkoxyl group, a nitro group,a halogen atom, a carboxyl group, NHCOR (wherein R represents a loweralkyl group), or

(wherein R and R" each represents a lower alkyl group, an aralkyl groupor an aryl group, R and R" being the same or different). Also, as theacid residual group X, there may be illustrated the following: halogenions, such as a chlorine ion or a bromine ion, a methyl sulfate ion, ap-toluene sulfonate ion, and the like.

Typical examples of the compound represented by the aforesaid generalformula are shown below:

Compound 1.

S l CH=CH-N( CH3) 2 H3O Compound 2.

' s NO; 021150 G CH=CH CH HSO a 4 N 12H5 Compound 3.

-o11=o111-1 om)2 (IJQH5 Compound 4.

O H -on=clnhmomn Cr OH; N

Compound 5.

Compound 6.

Compound 7.

Compound 8.

Compound 9.

Compound 10.

Compound 11.

Compound 12.

S I CH=CH-N (CH3):

Br- I I The development processing steps in the specification of thisinvention mean a prehardening process and a development process.

' It is most preferable that the light-exposed photographic silverhalide element be processed in a developer containing the compoundrepresented by the above-mentioned general formula and an aldehyde-typehardening agent but thelightexposed photographic element may beprocessed in a prehardening solution containing an aldehyde-typehardening agent and the aforesaid compound or may be processed in aprehardening agent and thereafter in a developer containing theaforesaid compound.

Furthermore, there is proposed another method wherein the compoundrepresented by the aforesaid general formula is incorporated in a silverhalide emulsion layer or a layer adjacent a silver halide emulsion layerand the light-sensitive element having said layer is processed in aprocessing solution containing the aldehyde-type hardening agent, whichmay be a hardening solution or a developer.

The amount of the compound represented by the aforesaid general formulagiving an effective antifogging effect in the case of incorporating thecompound in a developer containing the aldehyde-type hardening agent isusually 20-400 mg. particularly -300 mg. per 1 liter of developer. Thus,when the proportion is higher than 400 mg., the development isexcessively suppressed with the result that the sensitivity is reduced.On the other hand, when the amount is lower than 20 mg., the antifoggingeffect is very small. v

As the developer in the present invention, there may be employed analkaline aqueous solution containing a developing agent such asN-methyl-p-aminophenol, dihydroxybenzene, 1- phenyl-3-pyrazolidine,phenylenediamine or derivatives thereof.

The aldehyde-test hardening agent used in this invention is a compoundhaving at least one aldehyde group, such as formaldehyde, dimethylolurea, 'glyoxal, glutalaldehyde or the like, a sulfite thereof or abisulfite thereof.

As the formation of fog is effectively prevented by incorporating thealdehyde-type hardening agent and the compound represented by theaforesaid general formula in a processing solution simultaneously or inprocessing solutions separately according to the present invention, hightemperature development can be applied. Accordingly, since thewater-washing process, or the process for making the remaining unreactedaldehyde harmless, required in the conventional method, becomesunnecessary, the processing time is reduced, which is profitable forhigh speed processing.

The process of this invention may be applied to the developing processfor all photographic silver halide light-sensitive elements but may beparticularly applied to a high temperature and high speed processing forblack and white or color photographic elements.

The invention will further be explained by referring to the followingpreferable examples:

EXAMPLE 1 Development (39 C.) 25 seconds 50 seconds Fixing (39 C.) 5min. 5 min. Water washing (20 C.) [0 min. l0 min.

Developer A l-phenyl-B-pyrazolidone 1.5 g. Hydroquinone 20 g. Anhydroussodium sulfite 50 g. Sodium hydroxide 20 g. EDTA (2Na) 3 g.Glutalaldehyde (25%) I5 ml. S-Methylbenztriazole 0.2 g. Water to make 1liter.

Developer B 40 mg. of Compound 1 (described above) was added to 1 literof developer A. Developer C 170 mg. of Compound 1 was added to 1 literof developer The results are shown in FIGS. 1 and 2 of the accompanyingdrawings, which shows that the sample processed in developer B ordeveloper C showed less fog than the sample processed in developer A(control). Also, the gamma and the effective sensitivity in the former(B or C) were higher than in the latter EXAMPLE 2 Commercially availablehigh speed black and white negative photographic light-sensitive filmswere exposed by using a standard sensitometer and each of them wasdeveloped for 8 minutes at 20 C. in a developer shown in the followingtable prepared by adding only glutalaldehyde (control) or glutalaldehydeand Compound 7 (described above) to conventional developer D containingl-phenyl-3-pyrazolidone, hydroquinone, anhydrous sodium sulfite, sodiumcarbonate, and potassium bromide and having a pH of 10.3. The resultsare shown in the following table:

(A (8) Photographic property (mL/l.) (mg.) relative gamma fog intensityDeveloper E 10 100 0.50 2.10 Developer F 10 50 400 0.78 1.75 Developer G10 200 500 1.0 0.30

(Al' amount of 25%glutalaldehyde;

(8) amount of compound 7; Developer E control case.

As shown in the above table, the photographic properties are similar tothe results obtained in Example l.

EXAMPLE 3 The photographic films as in Example 2 were exposed by using asensitometer. One sample was then processed for 2 minutes inprehardening solution A (an aqueous solution having a pH of 10.3 andcontaining 10 ml. of 25 percent glutalaldehyde per 1 liter of thesolution) and another sample was processed for 2 minutes in prehardeningsolution B (an aqueous solution having a pH of 10.3 and containing 10ml. of 25 percent glutalaldehyde and 100 ml. of Compound 10 per 1 literof the solution). Thereafter, the samples were processed for 8 minutesat C. in developer D as in example 2. The results showed that theformation of fog in the sample processed in prehardening solution B wasmuch less than that of the sample processed in prehardening solution Aas in Examples l and 2.

EXAMPLE 4 Since a color development called coupler-in-developer typecolor development", i.e., a development using a color developercontaining a coupler, requires a long period of time for the processing,it is important that the emulsion layers of the color photographic filmto be processed maintain their strong mechanical properties during theprocessing. For this purpose, a method has usually been employed inwhich the mechanical strength of the emulsion layers is increased bysubjecting the layers to a prehardening treatment prior to the colordevelopment procedure. That is, the color development is usuallyconducted as follows:

Process l Temp.(C) Time (min.) I. Prehardening 27 l 2. Washing 27 l 3.First development 27 5 4. Washing 27 2 5. Reversal red exposure 6. Cyandeveloper 27 5 7. Washing 27 1 8. Reversal purple exposure 9. Yellowdevelopment 27 5 10. Washing 21 1 ll. Auxiliary development 27 1 l2.Washing 27 l 13. Magenta development 27 5 l4. Washing 27 l 15. Bleaching27 2 16. Fixing 27 2 17. Washing 27 2 l8. Drying When the prehardeningagent used in the above prehardening step was added to the firstdeveloping solution and the prehardening step and the washing step afterthe prehardening were omitted in order to shorten the processing time,the strong mechanical strength of the emulsion layers was maintainedduring the processing, but the coupling density was bitterly reduced andthe quality of the image was lowered, which made the development processunpracticable. However, it has been found that when an aldehyde-typehardening agent and the compound of this invention shown by the abovegeneral formula were added to the first development solution, theformation of fog could be effectively suppressed, and hence thedeveloping process could be simplified without reducing the couplingdensity and the mechanical strength of the emulsions while providing abetter image quality.

In other words, according to the process of the present invention, theprehardening step and the water washing step before the firstdevelopment in the so-called coupler-indeveloper type color developingsystem can be omitted, as well as reducing the period of time requiredfor finishing the first development by conducting the development at ahigh temperature without being accompanied with the aforesaid drawbacks,which make the process of this invention very profitable. An example ofthe improved steps for this development is shown below:

Process ll Temp. (C) Time (sec.) 1. First development 40 (hardeningdevelopment) 2. Water washing 40 30 First developer AN-methyl-p-aminophenol (112 sulfate) 20 g. Anhydrous sodium sulfite 90g. Hydroquinone 8 g. Sodium carbonate (mono-hydrate) 52.5 g. Potassiumthiocyanate l g.

Water to make 1 liter First developer B 20 ml. of 37% aqueous solutionof formaldehyde was added to 1 liter of first developer A.

Improved first developer 236 mg. of Compound 11 of this invention wasadded to 1 liter of First developer B.

Cyan color developer Anhydrous sodium sulfite 5.0 g.d-amino-J-methyl-N,N-diethylaniline 0.6 g. hydrochloride Sodiumcarbonate (mono-hydrate) 15.0 g. Potassium bromide 0.25 g. Potassiumiodide (0.1% aq. soln.) 2 ml. l,5-Dihydroxy-2,6-dibromonaphthalcne 1.2g. Sodium hydroxide 2.0 g.

' Water to make 1 liter Yellow color developer Anhydrous sodium sulfite5.0 g. 4-=mino-N.N-diethylaniline sulfate 2.5 g. Potassium bromide 1.0g. Potassium iodide (0.1% aq. soln.) 5 ml.m-Bcnzoyl4-(p-toluenesulfonamido)- 1.2 g. acetanilide Sodium hydroxide2.5 g. Water to make 1 liter.

Magenta color developer Anhydrous sodium sulfite 5.0 g. 4amino-3-methyl-N,N-diethylaniline 2.0 g. hydrochloride Potassium bromideI 0.2 g. l-phenyl-3-(m-nitrobenzylamino)- 1.4 g. S-pyrazolone Sodiumhydroxide 2.5 g. n-butylamide 5 ml. Water to make 1 liter Bleachingsolution Ferricyanide 100 g. Potassium bromide g. Borax 2 g. Boric acid1 g. Water to make l liter Fixing solution Sodium thiosulfate 150 g.Anhydrous sodium sulfile 10 g.

Water to make 1 liter The results are shown in the following table.

Relative sensitivity Maximum density Process Cyan Magenta Yellow CyanMagenta Yellow 1' 100 101 107 3. 50 3.80 3. 20 II 96 135 148 3. 50 2. 352. 70 III 101 96 111 3. 50 4. 00 3. 30

(Nora): I (control) employing first developer A. II (control) employingfirst developer B, III invention.

employing improved developer of this The results showed that usingProcess above, better photographic properties could be obtained than.

wherein 2 represents an atom necessary to complete a heterocyclic ring,R represents a member selected from the group consisting of a loweralkyl group and a substituted lower alkyl group of from one to fourcarbon atoms, Ar represents a member selected from the group consistingof a phenyl group and a substituted phenyl group, X represents an acidresidual group, and n is 0 or 1, said It being 0 when the compound formsan internal salt.

2. The method of claim 1', wherein the amount of said compound presentranges from about 20 to about 400 mg. per 1 liter of said developer.

3. The method of claim 2, wherein the amount of said compound presentranges from about to about 300 mg. per 1 liter of said developer.

4. The method of claim 1, wherein said aldehyde-type hardening agent isa member selected from the group consisting of formaldehyde, dimethylolurea, glyoxal and glutalaldehyde.

5. The method of claim 4, wherein said hardening agent is a memberselected from the group consisting of the sulfite and bisulfite adductof formaldehyde, dimethylol urea, glyoxal and glutalaldehyde.

6. The method of claim 1, wherein said developing agent is a memberselected from the group consisting of N-methyl-pamino phenol, dihydroxybenzene, l-phenyl-3-pyrazolidone, phenylene diamine and derivativesthereof.

7. The method of claim 1, wherein the substituted lower alkyl group is amember selected from the group consisting of a carboxymethyl group, afl-carboxyethyl group, a 'ycarboxypropyl group, a B-hydroxyethyl group,a fi-acetoxyethyl group, a fi-sulfoethyl group, 8-sulfobutyl group, a'y-sulfobutyl group and a methoxyethyl group.

8. A method of developing a photographic silver halide light-sensitiveelement, which comprises prehardening and developing an exposedphotographic silver halide light-sensitive element, wherein the elementis pro-hardened in a solution containing an aldehyde-type hardeningagent and subsequently processing in a conventional developer containinga compound represented by the formula:

R 1'. wherein Z represents an atom necessary to complete a heterocyclicring, R represents a member selected from the group consisting of alower alkyl group and a substituted lower alkyl group of from one tofour carbon atoms, Ar represents a member selected from the groupconsisting of a phenyl group and a substituted phenyl group, Xrepresents an acid residual group, and n is 0 or i, said n being 0 whenthe compound forms an internal salt.

9. The method of claim 8, wherein the amount of said compound presentranges from about 20 to about 400 mg. per 1 liter of said developer.

10. The method of claim 9, wherein the amount of said compound presentranges from about 100 to 300 mg. per 1 liter of said developer.

11. A method of developing a photographic silver halide light-sensitiveelement, said element containing in the silver halide emulsion layer orin a photographic layer adjacent to said silver halide emulsion layer acompound represented by the formula:

wherein Z represatsan afimrtecessaiyfizomplete a heterocyclic ring, Rrepresents a member selected from the group consisting of a lower alkylgroup and a substituted lower'alkyl group of from one to four carbonatoms, Ar represents a member selected from the group consisting of aphenyl group and a substituted phenyl group, X represents an acidresidual group, and n is 0 or 1, said It being 0 when the compound formsan internal salt, which comprises processing said exposed photographicsilver halide light-sensitive element with a processing solutioncontaining an aldehyde-type hardening agent.

12. The method of claim 11, wherein the processing solution is apro-hardener bath.

13. The method of claim 11, wherein the processing solution is aconventional developer bath.

14. A method of developing a photographic silver halide light-sensitiveelement, which comprises pre-hardening an exposed photographic silverhalide light sensitive element in a pre-hardening solution containing analdehyde-type hardening agent and a compound represented by the formula:

2. The method of claim 1, wherein the amount of said compound presentranges from about 20 to about 400 mg. per 1 liter of said developer. 3.The method of claim 2, wherein the amount of said compound presentranges from about 100 to about 300 mg. per 1 liter of said developer. 4.The method of claim 1, wherein said aldehyde-type hardening agent is amember selected from the group consisting of formaldehyde, dimethylolurea, glyoxal and glutalaldehyde.
 5. The method of claim 4, wherein saidhardening agent is a member selected from the group consisting of thesulfite and bisulfite adduct of formaldehyde, dimethylol urea, glyoxaland glutalaldehyde.
 6. The method of claim 1, wherein said developingagent is a member selected from the group consisting of N-methyl-p-aminophenol, dihydroxy benzene, 1-phenyl-3-pyrazolidone, phenylene diamineand derivatives thereof.
 7. The method of claim 1, wherein thesubstituted lower alkyl group is a member selected from the groupconsisting of a carboxymethyl group, a Beta -carboxyethyl group, a gamma-carboxypropyl group, a Beta -hydroxyethyl group, a Beta -acetoxyethylgroup, a Beta -sulfoethyl group, delta -sulfobutyl group, a gamma-sulfobutyl group and a methoxyethyl group.
 8. A method of developing aphotographic silver halide light-sensitive element, which comprisesprehardening and developing an exposed photographic silver halidelight-sensitive element, wherein the element is pre-hardened in asolution containing an aldehyde-type hardening agent and subsequentlyprocessing in a conventional developer containing a compound representedby the formula:
 9. The method of claim 8, wherein the amount of saidcompound present ranges from about 20 to about 400 mg. per 1 liter ofsaid developer.
 10. The method of claim 9, wherein the amount of saidcompound present ranges from about 100 to 300 mg. per 1 liter of saiddeveloper.
 11. A method of developing a photographic silver halidelight-sensitive element, said element containing in the silver halideemulsion layer or in a photographic layer adjacent to said silver halideemulsion layer a compound represented by the formula:
 12. The method ofclaim 11, wherein the processing solution is a pre-hardener bath. 13.The method of claim 11, wherein the processing solution is aconventional developer bath.
 14. A method of developing a photographicsilver halide light-sensitive element, which comprises pre-hardening anexposed photograPhic silver halide light sensitive element in apre-hardening solution containing an aldehyde-type hardening agent and acompound represented by the formula: